DE2453886A1 - METHOD OF ENCAPSULATING SUBSTANCES NOT MIXABLE WITH WATER - Google Patents

Description

CIBA-GEIGY AG, CH-4002 Basol

Case 5-9106 / +
Germany

Dr. F. For the first time. ·· Or. Il. Assrnsnn Dr. R.Koeni; ^r Ί .rner - LVi !. f ^: - · - K H-.i-I'a'iar D ,. F - ■■ · '-χ

'F ri .-, ... ·
β M On-, o " J i '., .., V.. </ Ill

Process for the encapsulation of substances immiscible with water

The present invention relates to a method for the encapsulation of substances immiscible with water.

The method is characterized in that the substance to be encapsulated is placed in a distribution means in the presence of a to the formation of a distribution

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An aqueous solution of a polyacrolein present as a hydrate or bisulfite adduct, which is capable of using an insoluble compound or dispersed acrolein copolymer and the hydrate or bisulfite adduct in the dispersion thus obtained with a water-soluble polyfunctional monomeric or polymeric hydrophilic compound and optionally additionally with a hardener or an aminoplast precondensate to form an insoluble capsule material.

A preferred embodiment of the invention Method consists in that the substance to be encapsulated in the distribution means in the presence of a dispersed aqueous solution of a bisulfite adduct of a polyacrolein or acrolein copolymer and the bisulfite adduct in the dispersion thus obtained with a water-soluble polyfunctional monomeric or polymeric hydrophilic Compound and optionally additionally with a carbonyl compound or an aminoplast precondensate Implementation of an insoluble capsule material. .

The present process uses a two-phase system j consisting of a liquid Musseren phase, which is referred to as a distribution agent, as well as a finely distributed, immiscible with the outer phase, substance to be encapsulated, which represents the inner phase,

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and a polyacrolein bisulfite adduct which is soluble in the outer phase or hydrate which serves to establish and maintain the finely divided state.

An aqueous medium, for example water, is preferably used as the distribution medium, in which the polyacrolein component and possibly other substances are dissolved. ·

Substances to be finely distributed according to the process according to the invention are solid, liquid or gaseous substances as well as substance solutions that are insoluble in water and with water as well do not react with the substances that make up the capsule wall.

Solids must be in the presence of the polyacrolein component dispersed and, if necessary, comminuted by grinding to such an extent that a stable dispersion is produced can be.

A wide variety of active ingredients, for example pharmaceuticals, can be used as dispersible solids Products including growth hormones and vitamins, Cosmetics, pigments, dyes, color formers, optical brighteners, textile auxiliaries, textile protection or finishing agents, fillers, waxes, fertilizers, plant regulators, Pesticides, such as insecticides, fungicides, antimicrobials, bio-silk, such as tick-killing agents also synthetic polymers that can be used as adhesives,

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Fragrances and flavorings, photo chemicals, water-insoluble Metal oxides, e.g. magnetic iron oxide, water-insoluble salts, etc. are used.

If the substance to be encapsulated, i.e. the inner phase, is a liquid, including? Substance solutions are understood, they may, as already mentioned, in the distribution medium, i.e. in the outer phase, not soluble or at least not miscible with it. In general it can be said that the outer and the inner Phase should be rummaged in such a way that neither substantial amounts of one phase are detached from the other, nor are unwanted ones chemical reactions take place.

■. As liquids to be emulsified, undiluted liquid active ingredients or solutions of liquid or solid active ingredients in suitable organic solvents be considered. In general, preference is given to liquid substances which have a high boiling point or are of low volatility are. However, the process also allows low-boiling liquids to be encapsulated.

Examples of liquid substances are petroleum fractions such as kerosene and naphtha, unbranched and branched, optionally halogenated paraffins, aromatic, optionally halogenated hydrocarbons such as benzene and alkylbenzenes, e.g. toluene, xylene, chlorobenzene, dichlorobenzene,

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Trichlorobenzene, Benzyl Chloride, BerizalchlGrid and analogues Bronic compounds, alkylated di- and polyphenyls, hydrogenated Terphenyls such as hexa- and dodecahydro-terphenyl, halogenated Di- and polyphenyls such as chlorinated diphenyls and polyphenyls, diphenyl diphenyl ether mixtures such as diphenyl diphenyl oxide mixtures, Methylenediphenyl, alkyl and hydronaphthalenes, Phosphoric acid esters such as tributyl and tricresyl phosphate, alkylated, optionally halogenated cycloaliphatics, Esters of higher fatty acids such as AethylmyristaL, Aethyloleate, Ethyl palmitate, vegetable oils such as corn oil, soybean beans, Olive oil, coconut oil, palm oil, castor oil, peanut oil, Rapeseed oil, sunflower oil, hemp oil, linseed oil, cotton seed oil, animal oils such as fish and whale oil, mineral oils, silicone oils or sperm oil. ■. '

It is particularly advantageous to use solutions of polyacrolein in aqueous solution as the polyacrolein component sulphurous acid or in aqueous bisulphite solution, in particular Sodium bisulfite solution.

Those used in the process according to the invention Polyacrolein bisulphite solutions are zv7eclaaässig by introducing them of sulfur dioxide in aqueous suspensions of polyacrolein, preferably at room temperature, during 1 to 12 Hours made. For the production of the emulsions, however, polyacrolein bisulfite solutions are also suitable by dissolving polyacrolein in aqueous sodium hydrogen

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sulfite solution can be obtained. In the bisulfite solutions The polyacrolein is usually the sulfurous acid adduct with the hydrated form of the polyacrolein Equal weight.

If in reactions with sensitive hydrophilic Compounds interferes with the presence of sulphurous acid, this can be done by dialysis, ion exchange or Oxidation can be removed with air. The polyacrolein

'.-- ■ - does not go into the insoluble state over, but remains as a reactive, stable polyacrolein llydrate in solution.

As a polyacrolein, for example, that from the article by J. Redtenbacher, Liebigs Ann, Chem. 47 (1843) 113 known disacryl, a under the Exposure to light, heat or catalytic quantities Oxygen on destabilized acrolein resulting polymer with average molecular weights between 60000 and 3C0000. In particular, however, radical polymers of acrolein with medium molecular weights are used between 500 and 300,000, preferably between 15,000 and 100,000, used, in particular by redox polymerization of acrolein in aqueous medium depending on the desired molecular weight in the absence or presence of emulsifiers such as sodium acetate, polyethylene oxide,

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Polyvinyl sulfonic acid sodium or polyacrolein bisulfite can be obtained.

In the absence of emulsifiers, average molecular weights can be between, depending on the reaction conditions 500 and 100,000 can be achieved, while average molecular weights in the presence of the emulsifiers mentioned above between 100,000 and 300,000 are available.

In the process according to the invention it is also possible to use copolymers of acrolein with other copolymerizable Vinyl compounds are used. Acrylamide, vinyl acetate and styrene, for example, are suitable as comonomers and acrylonitrile.

The component ratio in this copolymer! - seeds can be chosen arbitrarily, provided that the copolymers in aqueous sulfurous acid or are still soluble in alkali bisulfite solution with formation of adducts.

Preferred copolymers obtained by copolymerizing acrolein with the comonomers mentioned Redox systems obtained in an aqueous medium have, for example, the following compositions:

63 mol% acrolein / 37 mol% acrylamide 80 mole% acrolein / 20 mole% vinyl acetate S3 mol7o acrolein / 47 mol% acrylonitrile 66 mole percent acrolein / 34 mole percent acrylonitrile

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The carbonyl group content of the polyacrolein or acrolein copolymer solutions which can be used according to the invention is 20 to 100 mol percent, preferably 50 to 80 mol percent, based on the dissolved polyacrolein.

In principle, polyfunctional compounds are suitable as monomeric or polymeric hydrophilic reagents, which can be reacted in aqueous solution with the carbonyl groups of the polyacrolein component and as reactive Groups, preferably amino, hydroxyl or mercapto groups, but especially primary and / or secondary amino groups exhibit.

The term "reactive amino, hydroxyl and As used herein, mercapto group means any amino, hydroxyl or mercapto group in the hydrophilic ones Compounds that can take part in the reaction with the polyacrolein component. The amino group can for example also part of a hydrazine, carboxylic acid or. Sulfonic acid amides amidine, urea or Be carboxylic acid or sulfonic acid hydrazide group. In this respect, monomeric polyamines which contain at least two, preferably 2 to 5, have proven to be suitable functional amino groups contain, proven. For example, alkylene, cycloalkylene, arylene or heterocyclic polyamines, their amine functions

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are primary or secondary or can be contained in a heterocyclic nucleus, or mixtures thereof. If these polyamines are not water-soluble, their ammonium salts, for example hydrochlorides, can be used. In the case of the alkylene polyamines, these advantageously have 2 to 5 amino groups which are separated by straight-chain or branched alkylene groups having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. Useful polyfunctional Alkyienamine are for example ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, 1,2-propylenediamine, Dipropylentriämin, tripropylenetetramine, Dihydrox3 ⁷ dipropylenetriamine, dibutylenetriamine, tributylenetetramine, tetrabutylenepentamine, Dipentylentriamin, Tripentylentetramin, Tetrapentylenpentamin, dihexamethylenetriamine, Trihexamethylentetramin, Tetrahexamethylenpentamin as well as alkylene oxide adducts of di- or higher functional Alk} ⁷ lena mine such as adducts of 1 to 100 mols of ethylene oxide or propylene oxide with Di'äthylentriainin or Tri'äthylentetramin. It is also possible to use reaction products of epichlorohydrin with di- or higher-functional alkyleneamines such as, for example, reaction products of epichlorohydrin with triethylenetetramine in a molar ratio of 1: 1 to 5: 1.

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Examples of heterocyclic hydrophilic polyamines are piperazine, 1,4-bis- (3-aminopropyl) piperazine, 2-oxo-1,3-hexahydropyrimidine diethylamine to name among others.

Examples of aromatic and alicyclic hydrophilic polyamines are o-phenylenediamine, 4,4'-diaminodiphenylamine, 4,4'-diamino-dicyclohexylmethane, 2.2 ^! Bis- (4-aminccyclohexyl) propane or 4,4'-diamino-dicyclohexylamine are possible. '

Other polyfunctional, monomeric, hydrophilic compounds that react with carbonyl groups are aqueous Ammonia, hydrazine and at least two of these derived therefrom Reaction products containing groups and water-soluble aminoplast formers and aminoplast precondensates.

Aminoplast formers include methylolatable nitrogen compounds such as urea or thiourea compounds, 1,3,5-aminotriazines or cyanuric acid and aminoplast precondensates are products of the addition of formaldehyde to methylolatable nitrogen compounds Understood.

Suitable urea and thiourea compounds are, for example, urea, thiourea, substituted ureas such as alkyl or aryl ureas, alkylene ureas and diureas such as ethylene urea ₃ propylene urea, dihydroxyethylene urea, hydroxypropylene urea and

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Acetylenediurea, also dicyandiamide, dicyandiamides, Urons and ilexahydropyrimidones.

Examples of 1,3,5-aminotriazines that may be mentioned are: melamine and N-substituted melamines such as N-Buty! melamine, N-Trihalogenmethylmelamine, Triazone, ammeline, guanamines such as benzoguanamine, acetoguanamine, diguanamine and guanidines, the can be brought into a water-soluble form by conversion into corresponding ammonium salts.

The aminoplast precondensates are preferably the methylol compounds of the ureas mentioned and 1,3,5-arenotriazines into consideration. Among these compounds, N-methylolureas and! ^ - methylolmelamines are particularly special to highlight. Partial ethers of such methylol compounds e.g. with alkanols with 1 to 22 carbon atoms such as methanol, ethanol, n-propanol or n-O'ctadecanol be used.

Polyfunctional ones that can be used according to the invention polymeric hydrophilic compounds are, for example, water-soluble basic aminoplasts such as formaldehyde-dicyandiamide condensation products. In particular, condensation products of formaldehyde, dicyandiamide and urea are used in or the presence of a polyfunctional alkylene amine such as one of the above-mentioned alkylene polyamines is advantageous Results achieved. Suitable basic aminoplasts are above all formaldehyde-dicyandiamide-diethylenetriamine or formaldehyde-larnea-diethylenetriamine or formaldehyde urine

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substance-dicyandiamide-diethylenetriamine condensation products.

Suitable polymeric polyfunctional hydrophilic amine compounds are polymers of an alkyleneimine with 2 to 4 carbon atoms, which have a molecular weight of 500 to 80,000, preferably 10,000 to 40,000. These Polymers usually have a Brookfield viscosity at 20 ° C from 500 to 20,000 centipoise (Cp). Polyethyleneimines, polypropyleneimines, Poly-1,2-butyleneimine and poly-2,3-butyleneimine into consideration. Of all polyalkyleneimines, polyethyleneimine is preferred.

Of particular practical interest as hydrophilic polymers are the polyamido polyamines, which are produced by reaction are obtained from polyamines with polymeric carboxylic acids and by the addition of ethylene oxide or Addition of epichlorohydrin can be further modified. The polyamide polyamines suitably have an amine value im Range from about 200 to 650 mg of potassium hydroxide per Grams of polyamide amine.

As the polyamines that can be used for the preparation of the polyamide polyamines, aromatic Use polyamines or especially aliphatic polyamines, which can also contain heterocyclic structures, such as imidazolines,

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Polymeric carboxylic acids which are advantageously present in such polyamide amines are made by Polymerization of one or more unsaturated long-chain aliphatic or aromatic-aliphatic acids. or their esters or other derivatives which can easily be converted into the acid. Suitable examples such polymeric carboxylic acids are described in British patents No. 879,985 and 841,554.

The polymeric unsaturated carboxylic acids used here are advantageously aliphatic Ethylenically unsaturated di- to trimeric fatty acids. The polyamide amines are preferably made from polyalkylene polyarains and aliphatic, ethylenically unsaturated di- to trimeric fatty acids, which are derived from monocarboxylic acids derive with 16 to 22 carbon atoms. These monocarboxylic acids are fatty acids with at least one preferably 2 to 5 ethylenically unsaturated bonds. Representatives of this class of acids are e.g. oleic acid, Hiragonic acid, elaostearic acid, licanic acid, arachidonic acid, clupanodonic acid and especially linoleic and linolenic acid. These fatty acids can be obtained from natural oils, in which they mainly occur as glycerides.

The di- to trimeric fatty acids are given in a known manner by dimerization of monocarboxylic acids

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Kind received. The so-called dirner fatty acids always have a trimeric and a small content of monomeric acids.

Polyfunctional hydrophilic polymers used with preference are proteins, in particular scleroproteins such as gelatin or gelatin-like products, for example gelatin glue, glutin, tendon collagen, collagen breakdown products, Albumins such as blood albumin, egg albumin, serum albumins, globulins, catalase, casein, isinglass such as isinglass glue as well as fish glues obtained from fish bones and cartilage, protamines such as salmin and klupen; these polymers can as such oclei: also chemically modified, e.g. with Azetidin5.umverbindungen partially crosslinked, can be used. the named polymers contain both free amino and carboxyl groups. For example, in gelatine and gelatine-like products, the £ -amino group of lysine reacts, the amide group of an asparagine component and / or the guanidine group an arginine unit with the carbonyl functions of the polyacrolein component. As far as the polymers are difficult are water-soluble as in the case of casein, solutions in the presence of alkali, e.g. alkali metal hydroxides or carbonates or of tertiary amines and these are used in this way. In the case of the polyolein protein system, especially polyacrolein gelatin, highly hardened,

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but not friable capsule materials.

More hydrophilic, with the carbonyl functions the polyacrolein reacting "compound are hydrophilic polymers with reactive amino groups, the can also be used in the form of water-soluble salts such as the hydrochloride. This includes, for example Polyvinylaminhydroe.hlor id, poly-p-aminostyrene hydrochloride, Polyacrylic and polymethacrylamide, polyacrylic and polymethacrylic hydrazide or polystyrene-p-sulfhydrazide. These too Under certain circumstances, polymers can be further chemically modified, e.g. reacted with epichlorohydrin.

Itydroxylgruppe-containing polyfunctional hydrophilic Compounds ,, used according to the invention as crosslinkers can verden are, for example, polyalcohols such as polyvinyl alcohol, Polyallyl alcohol, also polyhydroxycarboxylic acids, ■ such as those obtained from polyacroleines by the Cannizzaro reaction are recoverable, furthermore cellulose and partially etherified or esterified cellulose derivatives and phenol-formaldehyde resins and the above-mentioned aminoplast precondensates with free hydroxyl and amino groups. Furthermore, polymeric Silicas, such as water glass, come into consideration.

• "The quantities used in the present process Required substances can vary within wide limits, depending on the intended use and the nature of the capsule material Requirements and the type of encapsulation

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Substances. For the encapsulation of liquid substances, it has proved to be expedient to 100 parts by weight of liquid from 33.5 to 335 parts by weight, preferably 67-200 parts by weight of insert 15 7 _o aqueous polyacrolein Bisulfitlb'sung. This corresponds to a polyacrolein solids amount of 5 to 50 parts by weight, preferably 10 to 30 parts by weight per 100 parts by weight of liquid to be encapsulated. -

15 7 ₀ polyacrolein bisulfite solution is understood to mean a solution which is 15% by weight of polyacrolein, not counting the amount of SOp required to produce the solution, which should be dosed so that the solutions are clear develop. In general, this amount is between 1 and 16% by weight of SOr in the solution. However, it is preferably between 2 and 10% by weight.

The amount of polyfunctional hydrophilic compound is also expediently 5 to 50 parts by weight, preferably 10 to 30 parts by weight per 100 parts by weight to be encapsulated Liquid. In the case of solid substances to be encapsulated, the lower limits of the amounts used are both Components, i.e. of the polyacrolein component and the hydrophilic polyfunctional compound, are generally somewhat higher than specified for liquids. For example, about 35 to 335 parts by weight, preferably 80 to

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200 parts by weight of the 15% polyacrolein bisulfite solution, which corresponds to a polyacrolein solids amount of 6 to 50 parts by weight, preferably 12 to 30 parts by weight. the The amount of hydrophilic polyfunctional compound is between 6 and 50 parts by weight, preferably 8 and 30 Parts by weight per 100 parts by weight of solid. The proportion of the substance to be encapsulated in relation to the total capsule mass can 50 to 95 percent by weight, preferably 60 to 90 percent by weight.

For encapsulation, the substrate provided as the capsule content is digested in the polyacrolein bisulfite or hydrate solution, diluted with water and then mixed with an aqueous solution of the hydrophilic polyfunctional compound acting as a crosslinker. Encapsulation takes place advantageously at p "values in the range from 2 to 10, but preferably at p" values between 5 and 8. With the polyacrolein-bisulfite) gelatine system, encapsulation is preferably carried out in the p "range from 8 to 10, whereby in this If the polyacrolein bisulfite solution is advantageously adjusted to the specified value with triethylamine and this solution is preferably used immediately to produce the emulsion. The erfindungsgem'äss usable Polyacarolein-bisulfite solutions are stable at p "values below 10, and up to 80 ⁰ C. The reaction temperature is generally between 5 and 80 ^° C. The encapsulation should preferably be carried out ^{at 20 to 60 ° C.}

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The polyacrolein bisulfite solutions produced with sulfur dioxide have a practically unlimited shelf life when stored closed and, depending on the SO ₉ content, have a ρ between 1 and 4. Alkali metals are particularly suitable for setting the ρ values desired for encapsulation hydroxides, bicarbonates and carbonates. In particular, however, tertiary bases, for example tertiary amines such as triethylamine, triethanolamine and pyridine, among others, are used. '

The capsule material is formed immediately after the polyacrolein bisulfite substrate emulsion has been combined and the hydrophilic polyfunctional crosslinking component, where the order of union has no influence. The capsule formation is the result of a precipitation reaction, in which the polyacrolein bisulfite or hydrate with the crosslinking component is converted to a polymeric compound that is insoluble in the external and internal phase. As far as the hydrophilic polyfunctional compound is also polymeric, becomes a composite polymer forming the capsule wall with co-crosslinking educated. By adding small amounts of aliphatic carboxylic acids with 1 to 6 carbon atoms, e.g. Formic acid, acetic acid, oxalic acid or citric acid can catalyze the crosslinking reaction. Are suitable also acidic hydrolyzing salts.

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The capsule material obtained as a dispersion can optionally be post-hardened or by post-encapsulation be reinforced. Halogenated aliphatic carbonyl compounds can optionally be used for additional post-curing with preferably 1 to 6 carbon atoms as hardeners be used. Suitable carbony compounds are for example monoaldehydes such as formaldehyde, acetaldehyde, propionaldehyde, acrolein and dialdehydes such as glyoxal, Methylglyoxal, glutaraldehyde and mucochloric acid.

Ketone compounds, for example dihydroxy ketones such as dihydroxyacetone, 1> 2- and 1,4-diketones such as 1,2-cyclohexanedione, can also be used as hardeners. Quinones, trioxane, tetroxane, hexamethylenetetramine, dianhydrides of tetracarboxylic acids, more functional Methansulronsäureester, compounds with multiple reactive Viaylgruppen as Vin3 ⁷ lsulfone, acrylamides, compounds with liiitidestens zx ^ ei -ie I fissile en heterocyclic rings such as ethylenimine and ethylene oxide as well as in the United States ! Azetidinium compounds described in U.S. Patent No. 3,634,399. The effect of the low molecular weight hardeners mentioned can be increased by adding known hardening accelerators, such as those described in German Patent No. 837 955, for example.

The low molecular weight hardeners listed above can also be used with high molecular weight e.g. polyaldehydes the periodic acid oxidation products of starch, as well as

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Metal salts such as chromium aluminum and zirconium salts are used. Hardening with metal salts leads to a certain Fragility and reduced stickiness of the capsule materials.

The capsule material present in aqueous dispersion can, if desired, be reinforced. For this the aminoplast precondensates already mentioned above, especially urea-formaldehyde or melamine-formaldehyde condensates, are suitable.

The production of such aminoplast precondensates is known and takes place, for example, by _{dissolving 1 mole of urea or melamine in an aqueous 5} about 37% formaldehyde solution that for 1 mole of urea 1.2 to 2 moles, for 1 mole of melamine approximately 3 to 6 moles of formaldehyde are omitted. If necessary, the resulting solutions are diluted somewhat with water and precondensed for some time at a p "value above 8.0 and a slightly elevated temperature. The aminoplast precondensate solutions obtained in this way are added to the polyacrolein bisulfite emulsion or the already preformed primary capsule suspension, it being important to ensure that the dispersity of the suspension is retained. Each capsule must be able to move freely, which is ensured by adding a sufficient amount of water. The resin shell is formed within a few hours at a p "value, that of urea-formaldehyde around 2.0, with melamine between. 4 and 6 lies. As a rule, stirring is not necessary. By tempe-

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ratürerhöhung to 40 to 6O ⁰ C, the resin formation can be accelerated. The finished capsules are isolated by filtering off and drying or by spray drying or freeze drying. The dry capsules form a fine, free-flowing powder.

Depending on the starting materials used, in particular the polyfunctional hydrophilic crosslinking component gas-tight capsules or capsules with a microporous and thus permeable capsule wall can be produced. in the in the latter case the capsules are liquid-tight, however not gastight. The gas tightness can be obtained by encapsulating with the addition of hardening agents performs. By adjusting the specific gravity of the substance to be encapsulated, for example by adding suitable substances Solvents, non-sedimenting microcapsules can be produced for certain application purposes can be of great importance.

The capsules obtained can be dispersed in a liquid, pressed into tablets, processed as surface coatings or in any other way in which the capsules are initially retained as such. '. ^!

The capsules are usually colorless and have a very long shelf life. Even temperatures of around 10O ⁰ C are effective

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does not interfere with the quality of the capsule, provided that it is not heat-sensitive Substances have been encapsulated. The encapsulated substance can be made out in several ways the capsules are released. Usually this is done mechanically by breaking the capsule wall by Applying pressure to this. Destruction of the capsule wall and thus the release of the contents can also be caused by shear forces, Friction, heat, ultrasound or enzymes can be achieved. If the capsule wall has a microporous structure, the encapsulated substrate can also be released to the outside through diffusion.

The microcapsules produced by the process according to the invention generally have a partial

, preferably 1 to 20 μ [

diameter from 1 to 500 ^ j / They are particularly suitable for the production of heat- and pressure-sensitive copier papers and recording materials. Here will be Color former solutions, optionally together with antioxidants and / or UV absorbers, encapsulated and the Capsule mass applied to paper or incorporated into the paper mass. Capsules with color former solutions can e.g. be applied to the back of a paper. The capsules are ruptured by pressure and the color former is released is transferred image-wise to the top of an underlying paper, which advises a developer

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is coated. This "process is called" Chemical Transfer " designated. .

In the so-called "chemical self-contained process", the encapsulated color former and the developer are applied in one layer on the paper, so that the top side of each sheet is permanently active. In the case of so-called "monoform" papers, the capsules and the developer are incorporated together into the paper pulp. Acid reacting kaolins, for example, are used as developers. Papers of this type coated with the capsules produced according to the invention are distinguished by excellent storage stability. After storage for 5 hours at ^100.degree. C., copies of unchanged good quality with sharp, non-smeared edges are obtained.

Percentages in the following production regulations and examples are by weight.

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Production of the polyacrolein bisulfite solutions

A. 328.4 g of polyacrolein (91.1% polyacrolein, 8.9% water) with an average molecular weight of 24500 and one after R.C. Schulz, H. Cherdron, W. Kern Makrom. Chem.

24 (1957) 141 certain reduced viscosity Ό / c- ^{K 6} spec

O, 2O3 (dl) g) produced by redox polymerization of acrolein with potassium persulfate (K2S2O0) and silver nitrate (AgNO-), are suspended in 1671.6 g of distilled water and by introducing 110 g of sulfur dioxide gas over the course of 3 hours with stirring solved. After filtration through a glass filter under reduced pressure gives a pale yellow polyacrolein bisulfite solution containing 16.35% polyacrolein and 5.6 X sulfur dioxide.

B. 342 g of polyacrolein (87.7 % polyacrolein; 12.3 % water) with an average molecular weight of 18,000 and a reduced viscosity determined by RC Schulz tj / c = 0.145 (dl / g), produced by redox polymerization of acrolein , are suspended in 1658 ml of distilled water and dissolved by introducing SO ₉ gas until the consistency is pasty while stirring on a vibromixer. After filtration through a glass filter under reduced pressure, a solution is obtained whose analytically determined polyacrolein content is 13.9% and SO ₂ 4.0 % .

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C. 173 g of a polyacroleine produced by redospolymerization with potassium persulfate / silver nitrate with a Schulz et al. certain-reduced viscosity / c = 0.163 (dl / g)

S p Θ 2

(M 20 000) were dissolved in 1.4 liters of distilled water after the addition of 112 g of sodium hydrogen sulfite with stirring at 50 ^° C. After filtration, 130 mg of FeSO were added, then sulfite was oxidized to sulfate by introducing oxygen with stirring with a vibromixer. The pH was kept between 5 and 6 at all times by adding 1 η sodium hydroxide solution. the oxidation is over when the pH value remains unchanged over a longer period of time. After adjusting to pH 6.8, the solution obtained was concentrated, then dialyzed to remove the neutral salts (cellophane dialyzer tube). The tube contents were then concentrated to an analytically determined concentration of 11.6% polyacrolein hydrate solution. The sulfur content of the solution was 0.1 %.

There is no need to remove the neutral salts, as they do not prevent composite polymer formation during microencapsulation influence.

D. In a SuIfierkolben 18.2 g (6,75.1O ~ ² moles) of potassium persulfate in 2 liters of distilled water and boiled were dissolved, and subsequently by passing nitrogen displaces the air. With 100 ml (1.5 moles) is charged freshly distilled acrolein and 60 ml (0,9PMoI) acrylonitrile and copolymerized at 20 ⁰ C.

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Addition of a solution of 11.4 g (6.70.10 mol) of silver nitrate in 50 ml of distilled water. After 12 hours, the precipitated copolymer was filtered off, washed with 2 liters of water, then taken up in a solution of 5 g of sodium thiosulfate in 4 liters of water and stirred for 3 hours. After renewed filtration with suction and washing was dried at 60 ⁰ C in a vacuum cabinet. 113 g (85.4% of theory) of a colorless copolymer with a according to Schulz et al. certain reduced viscosity / c = 0.256 (dl / g) and an analytically determined comonomer ratio of 64% acrolein and 36 % acrylonitrile.

54 g of the acrolein-acrylonitrile copolymer was slurried in 1 liter of distilled water, 40 g NaHSOo added and stirred at 50 ⁰ C. After 5 hours a clear, slightly yellow solution had formed, which was concentrated to an analytically determined content of 12.2% copolymer. The sulfur content of the solution was 2.8%.

E. In a manner analogous to that described under D, 100 ml (1.50 mol) of freshly distilled acrolein and 100 ml (1.52 mol) of acrylonitrile with 9.1 g (3.36.1O " ² mol) of potassium persulfate and 5.7 g (3,35.10 mole) of silver nitrate in 2 liters of distilled water and boiled The obtained copolymer copolymerized at 20 ⁰ C (143 g; 87% d.Th). containing acrolein and acrylonitrile in a ratio of 50% by Schulz et al The. Determined reduced viscosity / c was 0.70 (dl / g).

Spc2

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54 g of this acrolein-acrylonitrile copolymer have been g in 1 liter of distilled water after the addition of 36 NaHSOo at 50 ⁰ C gerlihrt was until a clear, slightly yellow solution. After filtration, the solution was concentrated to an analytically determined content of 12.6 "L of copolymer. The sulfur content of the solution was 2.6 %.

F. Analogously to D, 100 ml (1.50 mol) of freshly distilled acniein and 60 ml (0.91 mol) of acrylonitrile with 9.1 g (3.36.10 ~ ² mol) of potassium persulfate and 5.7 g (3.35.1 O ~ ² moles) of silver nitrate at 20 ⁰ C copolymerized. The copolymer obtained (115 g; 87 % of theory) had an analytically determined comonomer ratio of about 64 % acrolein and 37% acrylonitrile as well as a according to Schulz et al. certain reduced viscosity / c = 0.313

spec

(dl / g).

54 g of this acrolein-acrylonitrile copolymer were dissolved in 1 liter of distilled water after the addition of 28 g NaHSO., A clear solution with stirring at 50 ⁰ C, then the solution was concentrated to an analytically determined content of 10.7% copolymer.

G. 54 g mg under D described acrolein-acrylonitrile copolymer (/ c = 0.256 (dl'g) of distilled water were added after the addition of 24 g NaHSO ₃ at 50 ⁰ C under stirring, dissolved in 1 liter. After filtration, 50 of FeSO , added as an oxidation catalyst and by introducing oxygen, as described under C, a solution prepared which, after dialysis and concentration, had an analytically determined content of 13.9 "L acrolein hydrate-acrylonitrile copolymer and 0.15 ° L sulfur.

5 0 9 8 2 2/0880

example 1

50 g of the obtained according to manufacturing instruction A. Polyacrolein bisulfite solution are adjusted to pH 6.5 with 5% aqueous sodium hydroxyl solution. On that 50 g of an insecticide mixture are added using a high-speed stirrer consisting of 25 g of a compound of the formula

and 25 g of paraffin emulsified into it. The emulsion is diluted with 500 ml of distilled water while stirring continuously, and 500 g of a 1.2% gelatin solution are added. The resulting dispersion is transferred to another vessel, stirred further and mixed with 8 ml of 37% aqueous formaldehyde solution. A pH of 6.0 is set by adding glacial acetic acid. The reaction mixture is then ^{heated to 60 °} C. and cured at this temperature for 24 hours. After addition of 0.25 g sodium lauryl sulfate, the capsule mass is isolated by spray drying at an input temperature of "120 ⁰ C and an outlet temperature of 50 ⁰ C. The result is a color-imparting · loose powder that can be readily dispersed in water.

809822/0880 .. *

The capsule material dispersed in water shows no sedimentation. 95 "L of the capsule material has a particle size of 1-10 u, the main part is in the size range between 1 and 5 u. The capsule material consists of 95 % particles with a density of <1.0 and 80%

-3
Particles with a density> 0.96 (glad).

Example 2

114.5 g of the polyacrolein bisulfite solution prepared according to A are adjusted to pH 6.5 with 5% sodium hydroxide solution. 100 g of a 4% color former solution, prepared by dissolving 18 g of crystal violet lactone and 12 g of benzoyl-leukomethylene blue in 360 g of chlorinated diphenyl and 360 g of paraffin oil, are then emulsified with a high-speed stirrer. The emulsion is diluted with 1000 ml of water and, while stirring, adjusted to a pH of 5.8 with 1000 g of a 1.5% edible gelatin solution. The capsule mass is then heated to 40 ⁰ C, held for one hour at this temperature and 8 ml of 24-26 7 _o -igei glutaraldehyde solution and 6 ml of 37 7o-formaldehyde solution. After curing for 24 hours, the capsule material is isolated by spray drying. 119 g of a colorless, finely powdered capsule material are obtained which can be used for pressure-sensitive copier paper and which is excellent

• 509 822/0880

Shows copy-through effect. An aging test: ^{after 24 hours, the temperature at 105 °} C. shows a capsule material with an unchanged copying effect. '

Example 3

57.3 g of the polyacrolein bisulfite solution prepared according to A are adjusted to pH 6.5 with 5% sodium hydroxide solution. Then, 50 g of a 4% dye solution - 40 g of 3-methyl-2,2-spiro-di (benzo) -chromen dissolved in 960 g of partially hydrogenated terphenyls (Sp 340-396 ⁰ C) - hineinemulgiert with a rapid stirrer. After the emulsion has been diluted with 500 ml of water, 500 g of a 1.5% edible gelatin solution are added, the capsule being formed by precipitation of a composite polymer. The capsule suspension is ^{heated to 40 °} C. with stirring, kept at this temperature for one hour, mixed with 10 g of 37% strength formaldehyde solution and hardened at a pH of 8 for 12 hours. The capsule mass is then adjusted to pH 5 with acetic acid and spray-dried. 60.5 g of dye capsules are obtained with a good copy effect when used in pressure-sensitive copy material. An aging test of 24 hours at 105 ^° C. then showed an unchanged copying effect of the capsules.

509822/0880

Example 4 . .

57.3 g of A according Polyacroleinbisulfitlösung produced are provided with 5 7 _o strength sodium hydroxide solution to pH 6.5. Then 50 g of a mixture consisting of 0.5 g of 4,2 ', 4'-trichloro-2-hydroxy-diphenyla'ther and 49.5 g of ethyl oleate are emulsified. The emulsion is diluted with 500 ml of water, a solution of 70 g of edible gelatin in 430 g of water is added and the pH is adjusted to 6 with 5% sodium hydroxide solution while stirring. Immediately after the addition of the gelatin solution, the capsule wall forms with precipitation of a polymer compound. The capsule mass is heated to 60 ⁰ C, treated with 8 ml 37% formaldehyde solution and cured 16 hours. After cooling to room temperature, the capsule material is spray-dried. 61 g of the encapsulated antimicrobial are obtained.

Example 5

59.7 g of the polyaerolein bisulfite solution prepared in accordance with A. are adjusted to pH 6.5 with 5% sodium hydroxide solution. Then 50 g of an insecticide mixture the composition given in Example 1 'is emulsified in using a high-speed stirrer. After diluting

509 822/0880

.32- 2453885

a solution of 37.5 g of a water-soluble diethylenetriamine-adipic acid-epichlorohydrin reaction product according to British patent specification No. posed, whereby the capsule formation takes place. The resulting capsule suspension is heated to 60 ⁰ C, with 20 ml 3Ü% solution of formaldehyde was added and cured for 24 hours. After filtering off, washing with 500 ml of water and air drying, 62 g of capsule material are obtained. This is well permeable and shows a retarded release effect for the encapsulated active substance.

Example 6

- 50 g of the polyacrolein bisulfite solution prepared according to A are with 5% sodium hydroxide solution adjusted to pH 7. 50 g of an insecticide mixture of the composition given in Example 1 are then added emulsified in with a whisk and then The emulsion is diluted with 500 ml of water. While continuing to stir "A solution, adjusted to pH 6.5 with acetic acid, of 7 g of diethylenetetramine in 500 ml of water is added, with the capsule material fails. After 30 minutes, 30 g of 37% formaldehyde solution are added and the reaction mixture

. " ⁵ '509822/0880

kept mixed at 60 ^° C. for 24 hours. After filtering off, washing with 500 ml of water and drying in air, 63 g of a lemon-yellow capsule material are obtained (with a porous capsule wall and a delayed release effect for the encapsulated active substance

Example 7 .

50 g of the polyacrolein bisulfite solution prepared according to A are with 5% sodium hydroxide solution adjusted to pH 6.4. Then 50 g of an insecticide

Mixture of the composition given in Example 1 is emulsified in with a Schnei! stirrer, the emulsion is then diluted with 500 ml of water. To this end, 100 g of a 9% solution of a condensation product of 42 g of dicyandiamide, 121.6 g of 30% formaldehyde solution and 25.8 g of diethylenetriamine are added in 937 g of water and the pH is adjusted to 6.0 with acetic acid. The capsule is formed by precipitation of a polymer compound. The reaction mixture is ^{kept at 60 °} C. for 18 hours, then the capsule material is filtered off, washed with 1000 ml of water and air-dried. 63 g of microencapsulated insecticide are obtained. The capsule material is microporous; the capsule contents are released in a retarded manner.

. 509822/0880

Example 8

113.3 g of the polyacrolein bisulfite solution prepared according to A are adjusted to pH 6.5 with 10% sodium hydroxide solution. 100 g of a mixture are then added consisting of 130.2 g of an insecticide of the formula given in Example 1 and 119.8 g of paraffin with a high-speed stirrer stirred in, the emulsion then diluted with 1000 ml of water. While stirring one on one pH value of 6.5 made up of 5 g of a polyethylene solution

Un 1000 ml / imine having a viscosity at 20 ⁰ C 10000-20000 Cp of water is added, and by precipitating a composite polymers, the capsule formation occurred, then a \ i orkondensat of 30 g of melamine and 62 g of 37% formaldehyde solution. was added and continued at 60 ⁰ C. The reaction mixture is ^{kept at 60 °} C. for 20 hours and then cooled to room temperature. Thereafter, the capsule material is filtered off, washed with 1000 ml of water and finally dried at 40 ⁰ C. 158 g of a lemon-colored, slightly agglomerated capsule material are obtained.

Example 9

114.5 g of the polyacrolein bisulfite solution obtained according to A are adjusted to pH 6.5 with 10% sodium hydroxide solution. Then 100 g of a mixture

... '. 50 9822/08 80

consisting of 312.5 g of an insecticide of the formula given in Example 1 and 187.5 g of paraffin emulsified in with a rapid mixer, the emulsion then diluted with 1000 ml of water. With continued stirring, a solution of 51.5 g of melamine-formaldehyde precondensate in 1000 ml of water is added at 60 ^° C. and the reaction mixture is adjusted to pH 6.5 with glacial acetic acid. After 20 hours of hardening at 60 ^° C., the capsule material obtained is filtered off, washed with 1000 ml of water and ^{dried at 40 °} C. in a gentle stream of air. 152.6 g of capsule mass with good chemical resistance are obtained.

Example 10 ""

65 g of the obtained according to manufacturing method B. Polyacrolein bisulfite solution are adjusted to pH 8.0 with triethylamine. Then 50 g of an insecticide mixture of the composition given in Example 1 are emulsified in using a high-speed stirrer. The emulsion is diluted with 600 ml of water and, while stirring, a solution of 7.0 g of edible gelatin in 450 g of water, which has also been adjusted to pH 8 with triethylamine, is added. Under further stirring, the dispersion is heated to 60 ° C, with 8 ml of 37 7o-strength aqueous formaldehyde solution are added and cured for 22 hours at 60 ⁰ C, the pH

509822/088 0

is maintained at 8.0 by adding 5% sodium hydroxide solution. After spray-drying at an inlet temperature of 150 ⁰ C and outlet temperature of 75-8O ° C 64 g of a colorless, friable capsule material with a particle size between 1 and 6 and obtained.

Example 11 "· ...

49 g of the polyacrolein bisulfite solution prepared in accordance with regulation A are adjusted to ρ «5.4 with 5% strength aqueous sodium hydroxide solution, then 50 g of an insecticide mixture consisting of 25 g of the compound of formula (1) (96%) and 25 g of paraffin oil are added and emulsified. After the emulsion has been diluted with 600 ml of distilled water, a solution of 8 g of edible gelatin in 392 ml of distilled water is added and the batch is stirred ^{at 40 ° C. for one hour.} Then • is with 5% aqueous sodium hydroxide solution. set a p "of 7.5 and cured at this p _H for 22 hours. After spray-drying the reaction product, 62 g of a free-flowing capsule material with a particle diameter in the range from 1 to 5% are obtained.

509822/08 8 0

Example 12

The procedure is as in Example 11 with the difference that instead of the insecticide mixture, a dye-forming solution consisting of 25 g of chlorinated biphenyl, 25 g of paraffin oil, 1.2 g of crystal violet lactone and 0.8 g of benzoylleuco-methylene blue is used. After spray-drying the reaction product, 63.5 g of a capsule material with discrete microcapsules, the diameter of which is in the range from 2 to 10 μ , are obtained. The capsule material obtained in this way can be used for carbonless and copier papers.

509822/0880

Example 13

57.3 g of the polyacrolein bisulfite solution prepared according to A are adjusted to p "7.5 with triethylamine. Then, 50 g of a 4% color former solution - 40 g of 3-methyl-2,2-spiro-di- (benz) -chromen dissolved in 960 g of partially hydrogenated terphenyls (melting point: 340-396 ⁰ C) hineinemulgiert with a Schnellriihrer, until a droplet size of about 1 to 5 μ is reached. It is then diluted with 400 ml of water.

10 g casein are dissolved after 12 stUndigem swelling in 70 ml of water at 50 ⁰ C with the addition of triethylamine. When the solution no longer contains gel particles, it is diluted with 500 ml of water at 50 ° C. The emulsion described above is allowed to run in with stirring and cured for 22 hours at 50 ^° C., the p ^ value of the dispersion being kept at 7.5. After spray drying at an inlet ^{temperature of 150 °} C., 67 g of dye capsules with a capsule diameter of 2 to 10 μm for use in pressure-sensitive copying material are obtained.

509822/0880

Example 14

Using a rapid mixer, 60 g of a dye solution of the composition given in Example 2 were emulsified into 100 g of the acrolein-acrylonitrile copolymer bisulfite solution described under D, and the emulsion was then diluted with 700 ml of water. Then 180 g of a 5% aqueous solution of polyacrylic hydrazide (prepared by reacting polyacrylic acid ethyl ester (= 0.18 (dl / g); M = 30,000) with hydrazine according to Kern and Schulz, Angew. Chem. J69_ (5 ) (1957) 155) was added. A pH of 7 was set with 1 η sodium hydroxide solution and the batch was cured for 12 hours while stirring on a vibromixer. Spray drying at an inlet temperature of ^{120 ° C. and an outlet temperature of 50 °} C. gave 79 g of a capsule material consisting of discrete microcapsules with a particle diameter between 1 and 10

Example 15

In 100 g of the acrolein-acrylonitrile copolymer bisutfit solution described under F. 60 g of a dye solution of the composition given in Example 2 were emulsified with the aid of a rapid mixer, the emulsion is then diluted with 700 ml of water. Then the emulsion was stirred with a vibromixer with a solution of 8 g of edible gelatin in 152 ml of water and adjusted with 1 η sodium hydroxide solution to a pH of 7.5, which is

509822/0880

The course of the 12-hour hardening at room temperature is maintained by adding more sodium hydroxide solution. The capsule dispersion was sprllhgetrock.net at an inlet temperature of 125 ⁰ C and an outlet temperature of 65 ° C to obtain 74.5 g of a discrete microcapsules (particle diameter of between 1 and 10) existing preparation was obtained.

Example 16

60 g of the dye solution of the composition given in Example 2 were emulsified in 100 g of the acrolein-acrylonitrile copolymer bisulfite solution described under E, and the emulsion was then diluted with 700 ml of water. This was followed by stirring at the vibromixer a solution of 8 g of casein in 152 ml of water to which a few drops Triä'thylamin had been added, was added and cured for 12 hours at 50 ⁰ C and a pH of 7.5. After spray drying under the conditions given in Example 15, 76 g of a preparation consisting of discrete microcapsules (particle diameter between 1 and 8) were obtained.

Example 17

60 g dye solution of the composition given in Example 2 were in 100 g of the acrolein hydrate-acrylonitrile copolymer solution described under G. emulsified in with the aid of a high-speed stirrer, the emulsion diluted with 500 ml of water and then under

509822/08 80

Stirring on the vibromixer with a solution of 10 g of polyvinyl alcohol (M = 22,000) in 100 ml of water. With 1 η hydrochloric acid a pH of 3 was set, precured at 40 ° C. for one hour, then below that given in Example 15 Spray dried conditions. 77.5 g of a preparation consisting of discrete microcapsules were obtained. Particle diameter: 1-15

Example 18

60 g of a dye solution of the composition given in Example 2 were emulsified in 100 g of polyacrolein hydrate solution (solution C) with the aid of a high-speed stirrer, and the emulsion was then diluted with 700 ml of water. Under further stirring at vibromixer C was heated to 60 ^0, then 160 g added to the process given in Example 14 5% Polyacrylhydrazidlösung. After adjusting a pH of 7.0 with 1 η sodium hydroxide solution (:; initial temperature 125 ° C: 6O ⁰ C inlet temperature) was obtained after a curing time of 15 hours · spray dried. 72 g of a slightly yellow capsule preparation consisting of discrete microcapsules (particle diameter 1-15) were obtained.

Example 19

60 g of dye solution of the composition given in Example 2 were emulsified into 100 g of polyacrolein hydrate solution (solution C) with the aid of a Sehnell stirrer, and the emulsion was then diluted with 700 ml of water. After heating the batch to 60 ⁰ C were under

509822/0880

Continue stirring on the vibromixer 225 g of a 4% aqueous Isinglass solution (isinglass glue) was added and a pH of 7.5 was set with 1 η sodium hydroxide solution, which was maintained throughout the Curing time (15 hours) is kept at this value. Thereafter, under those given in the previous example Spray-dried conditions, whereby 76.5 g of a discrete microcapsules (particle diameter 1-10) existing capsule preparation was obtained.

Example 20

60 g of Santosol 340 (HB 40) were emulsified into 100 g of polyacrolein hydrate solution C using a high-speed stirrer, the The emulsion is then diluted with 700 ml of water. Then 200 g of a 9% aqueous sodium silicate solution (water glass), the pH of which was previously reset to pH 8 with 1 η hydrochloric acid, added, by further addition of hydrochloric acid to the emulsion, a pH of 4 was set at this. After about 15 hours, stable, discrete microcapsules formed by spray drying at an inlet temperature of 130 ° C and an outlet temperature of 65 ° C could be isolated with a yield of 83.5 g. The particle diameter of the capsules was between 1 and 15

509822/0880

Example 21

Using a high-speed stirrer, 60 g of a dye solution of the composition given in Example 2 were emulsified into 100 g of polyacrolein hydrate solution C, and the emulsion was then diluted with 500 ml of water. To the heated to 70 ⁰ C under emulsion were then Weiterrlihren the vibromixer 120 g of a 10% aqueous polyvinyl alcohol solution (M = 22000) and a pH of 3 with 1 η hydrochloric acid. After einständigem pre-curing was at an inlet temperature of 130 ⁰ C and an outlet temperature of 60 ° C spray-dried with a 77.5 was obtained from discrete microcapsules having a particle diameter of 1-15 existing preparation.

Example 22

35 g of polyacrolein hydrate solution C and 160 g of 9.6% polyvinyl alcohol solution (M = 22,000) were mixed together homogeneously, then 50 g of a 4% solution of 3-methyl-2,2-spiro-di (benzo ) -chromen emulsified in Santosol 340 (HB 40) and the emulsion diluted with 500 ml of water. A pH of 4 was adjusted by adding 2 η sulfuric acid, vorgehartet 1 hour with stirring and then vibromixer at an inlet temperature of 130 ⁰ C and an outlet temperature

509822/0880

spray-dried from 60 ° C, with 63 g of a capsule preparation (Particle diameter 1-15).

A coated capsule dispersion and dried carbonless paper also showed after 5 hours of aging at 100 ⁰ C practically unchanged copy capability.

509822/0880

Claims (1)

Claims 1. A method for encapsulating substances immiscible with water, characterized in that the substance to be encapsulated in a dispensing agent in the presence an aqueous solution capable of forming a compound insoluble in the distribution agent as Hydrate or bisulfite adduct present dispersed polyacrolein or acrolein copolymer and the hydrate or bisulfite adduct in the dispersion thus obtained with a water-soluble polyfunctional monomer or polymer hydrophilic compound and optionally additionally with a hardening agent or an aminoplast precondensate reacts to form an insoluble capsule material, 2. The method according to claim 1, characterized in that that the substance to be encapsulated in the distribution medium in the presence of an aqueous solution of a bisulfite adduct dispersed a polyacrolein or acrolein copolymer and the bisulfite adduct in the dispersion thus obtained with a water-soluble polyfunctional monomeric or polymeric hydrophilic compound and optionally additionally with a carbony compound or an aminoplast precondensate reacted to form an insoluble capsule material. '509822/0880 3. ■ The method according to claim 2, characterized in that a bisulfite solution of a polyacrolein with an average molecular weight of 500 to 300,000, preferably 15,000 to 100,000 is used. 4. The method according to claim 2, characterized in that a bisulfite solution of a copolymer
of acrolein with another copolymerizable
Vinyl compound used. 5. The method according to any one of claims 1 to 4, characterized characterized in that the polyfunctional monomeric hydrophilic compounds are polyamines with at least two functional amino groups used. 6. The method according to any one of claims 1 to 5, characterized in that the polyfunctional hydrophilic Compounds alkyleneamines with 2 to 5 amino groups, by straight-chain or branched alkylene groups with 2 to 6 carbon atoms are separated is used. 7. The method according to any one of claims 1 to 4, characterized characterized in that the polyfunctional monomeric hydrophilic compounds are methylolatable or methylolated nitrogen compounds used. 509822/0880 8th. . Process _/ according to one of Claims 1 to 4, characterized in that the polyfunctional polymeric hydrophilic compounds used are polyalkyleneimines with an average molecular weight between 500 and 80,000, preferably 10,000 and 40,000. 9. The method according to any one of claims 1 to 4, characterized in that the polyfunctional polymers hydrophilic compounds water-soluble basic aminoplasts are used. . 10. The method according to any one of claims 1 to 4, characterized in that the polyfunctional polymers hydrophilic compounds polyamide amines, obtained by polycondensation of polymeric carboxylic acids with polyamines have been used. 11. The method according to claim 10, characterized in that that a polyamide amine with an amine value in the range of 200-650 mg of potassium hydroxide per gram of polyamide amine is used as polyfunctional polymeric hydrophilic compound used « Method according to one of Claims 1 to 4, characterized characterized as being polyfunctional polymers 509822/0880 hydrophilic compounds hydrophilic polymers with reactive amino groups or their water-soluble salts are used . 13. The method according to any one of claims 1 to 4, characterized in that the polyfunctional polymers hydrophilic compounds protein substances, preferably gelatine or gelatine-like products are used. 14. The method according to any one of claims 1 to 13, characterized characterized in that one aliphatic carbonyl compounds with at most. 6 carbon atoms as hardening agent used. · ' 15. The method according to any one of claims 1 to 13, characterized in that urea-formaldehyde or Melamine-formaldehyde condensates as aminoplast precondensates used. 16. The method according to any one of claims 1 to 15, characterized in that the distribution agent is water used. 5 09822/0880 17 '' Method according to one of claims 1 to 16, characterized characterized in that the substance to be encapsulated is liquid or solid active ingredients or also in organic Solvents used active ingredients. 18. The according to the method of any one of claims 1 to available capsule sizes. 19. Use of aqueous solutions of a polyacrolein or acrolein copolymer present as a hydrate or bisulfite adduct in combination with water-soluble polyfunctional monomeric or polymeric hydrophilic compounds and optionally additionally with hardeners or an aminoplast precondensate for encapsulating with water not miscible substances. $ 09822/0880